Journal of Non-Crystalline Solids 307310 (2002) 470480

www.elsevier.com/locate/jnoncrysol

Volume recovery of polystyrene: evolution of the

characteristic relaxation time
P. Bernazzani, S.L. Simon *

Department of Chemical Engineering, Texas Tech University, Box 43121, Lubbock, TX 79409-3121, USA

Abstract

We have developed a new experimental technique that uses intermittent temperature perturbations during volume
recovery in order to obtain quantitative information concerning the evolution of the characteristic relaxation time for
volume during structural recovery. The experiments are analogous to the intermittent creep experiments developed by
Struik. Using an automated capillary dilatometer and a polystyrene sample, the time-temperature history dependence
of the characteristic relaxation time for volume was investigated. Our preliminary results show that for the set of
temperature down jumps and memory experiments investigated, the characteristic relaxation time appears to depend
only on the instantaneous state of the material. However, the results are not totally consistent with the ToolNaray-
anaswamy model/KovacsAklonisHutchinsonRamos model.
2002 Elsevier Science B.V. All rights reserved.

1. Introduction perfect quench from an initial temperature T0

Polymer glasses have been the object of a great
deal of interest in the last 50 years [115]. Math-
ematical models of structural recovery have been
developed, including Moynihans formulation [12]
of the ToolNarayanaswamy model (TNM) [13,14]
and the KovacsAklonisHutchinsonRamos
model (KAHR) [15], the latter of which is essen-
tially equivalent to the TNM model. These math-
ematical models are able to describe the
manifestations of glassy behavior [6,8,1214]. The
TNM model uses the ctive temperature Tf to
describe the changing structure of the glass. For a
*
Corresponding author. Tel.: +1-806 742 3553; fax: +1-806
742 3552.
E-mail address: sindee.simon@coe.ttu.edu (S.L. Simon).
above Tg to an aging temperature, Ta , below Tg , the
ctive temperature is given by

 R t b 
Tf T0 DT 1
e

dt
0 s ; 1
where Tf is dened as the temperature at which
a material would reach equilibrium if heated or
cooled along the glass line, DT Ta
T0 , t is the
time elapsed following the jump, s is the charac-
teristic relaxation time describing the recovery and
b is a parameter with values between 0 and 1 that
accounts for the non-exponentiality of the recov-
ery. The non-linearity of the recovery process is
accounted for by allowing s to be a function of
structure (Tf ), as in the following equation devel-
oped by Narayanaswamy [14] and modied by
Moynihan [12]:

0022-3093/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 2 ) 0 1 4 6 3 - 1
 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480
xDh 1
xDh
lns lnA ; 2
RT RTf
where lnA is a constant, R is the gas constant, x
partitions the dependence of s between tempera-
ture and structure (Tf ) and Dh is the apparent ac-
tivation energy. We note that although s is referred
to as a relaxation time, it is actually a retardation
time.
In contrast to the TNM model which uses the
ctive temperature as a measure of structure, the
KAHR model describes structure in terms of a
departure from equilibrium (d):
V
V1
d ;
V1
where V is the instantaneous specic volume and
V1 is the equilibrium specic volume. The depar-
ture from equilibrium (d) can easily be converted
to Tf , and vice versa, by the following equation:
d shown in Fig. 1. After a down jump from T0 above
Tf Ta ; 4
Da
where Da is the change in thermal expansion co-
ecient from the equilibrium to the glassy states.
Using the relationship between Tf and d in Eq. (4),
which assumes a perfect quench (otherwise To
should be replaced by Tf0 in the equation), Eq. (1)
can be rewritten in terms of d:
" Z
t b #
dt
d d0 exp
; 5
0 s
where d0 is the departure from equilibrium im-
mediately after an ideal quench.
Although both the TNM/KAHR model can
describe the phenomena associated with the ki-
netics of the glass transition, they are unable to
simultaneously describe experiments performed
over a wide range of thermal histories and their
predictive capability is thus limited [6,8,1625].
Simple corrections to the model provide little im-
provement [8,19,23,25,26].
A basic assumption common to the TNM and
KAHR models is that the characteristic relaxation
time, s, depends on the instantaneous state of the
material, and not on its time-temperature history.
Struik tested this assumption for polycarbonate,
polyvinyl chloride and for polystyrene (PS) [27].
471
He separately measured the creep response and
volume recovery during physical aging and then
cross-plotted the creep shift factor versus volume.
He concluded that the creep shift factor depended
only on the instantaneous volume of the sample.
However due to scatter in the data, which may
have arisen in part from measuring the properties
separately, his conclusions are arguable. Further-
more, the fact that the evolution of the charac-
teristic relaxation time for volume may not be the
same as that for the mechanical relaxation due to
the possibility that there may be dierent time
scales for dierent properties [2844] suggests the
need to directly measure the evolution of the
3 characteristic relaxation time for volume.
At this point it would be benecial to review the
experimental methodology used by Struik [1] to
measure the instantaneous creep response during
physical aging using sequential stress perturbation
experiments. A schematic of Struiks experiment is
Tg to Ta below Tg , intermittent stress perturbations
are applied while the resulting strain is measured.
The intermittent stress perturbations are 10 times
shorter than the aging time, te , so that the material
does not signicantly age during the perturbation.
The time between each perturbation must be such
that the recovery from the last perturbation does
not overlap the next perturbation. The recovery
time is generally two or three times the aging time.
Each stress perturbation or creep experiment gives
a snapshot of the creep response at a particular
aging time.
Analogous to Struiks methodology we have
developed a new experiment to directly study the
characteristic relaxation time for volume during
aging. It makes use of intermittent temperature
perturbations during volume recovery to obtain
quantitative information concerning the evolution
of the characteristic volume relaxation time during
structural recovery. Fig. 2 shows the methodology
developed. Intermittent temperature perturbations
are performed after an initial temperature jump
from T0 above Tg to an aging temperature, Ta ,
below Tg . Each temperature perturbation yields a
snapshot of the volume response at a particular
aging time. As a consequence, the characteristic
relaxation time for volume, s, can be obtained as a
472 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480

Fig. 1. Experimental methodology used by Struik to measure the evolution of the mechanical characteristic relaxation time during
aging.

Fig. 2. Experimental methodology used in this paper to measure the evolution of the characteristic relaxation time for volume during
aging.

function of aging time. Again, the sequential per-
turbations are short compared to the aging time,
such that the material does not age signicantly
during the perturbations. Hence, the method al-
lows the direct determination of the characteristic
relaxation time for volume recovery during the
aging experiment.
The paper is organized as follows. First, we
detail the experimental methodology used in the
work, including the thermal histories performed
 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480
and the method of data analysis. We include the
results of TNM/KAHR model calculations, which
show that the methodology and data analysis are
consistent with the model. We follow with pre-
liminary results, discussion, and conclusions.
2. Methodology
2.1. Material
The material studied is a PS, Dylene 8 from
Arco Polymers. The number-average molecular
weight is 92 800 g/mol; the weight-average molec-
ular weight is 221 000 g/mol; the z-average mo-
lecular weight is 423 000 g/mol [32]. It was
obtained in pellet form.
A dilatometric sample was obtained by sinter-
ing the polystyrene pellets in a 0.5-in. diameter
tubular mold at 120 C under vacuum to minimize
voids. A 0.125-in. hole was then drilled through
the center to allow a better contact with the mer-
cury in the dilatometer. The nal mass of the
sample was 5 g.
2.2. Dilatometric studies
A capillary dilatometer, based on the design of
Plazek, was used [45]. The dilatometer consists of a
stainless steel bulb containing the sample and
mercury as the surrounding uid. A precision
bored Pyrex capillary tube is axed to the bulb. In
order to automate the system, an aluminum oat
is placed on top of the mercury and attached to a
linear variable dierential transformer [46]. A
computer records the output. The data acquisi-
tion is controlled using Labviewe software from
National Instruments. To eliminate recurring vi-
brations a ltering technique was used: a Fast
Fourier Transform of the data was performed
every second over 200 data points and the higher
frequencies were eliminated. The inverse transform
was then performed with minimal lag variation
[47]. The result is analogous to a low pass lter.
The resolution of the system is better than 0:4 
10
5 cm3 /g.
Temperature jumps from equilibrium to the ag-
ing temperature were accomplished by rst equili-
473
brating the sample and dilatometer in a silicon oil
bath maintained at a temperature above Tg and
then quickly transferring the dilatometer to a bath
maintained at the aging temperature. For the tem-
perature perturbations of 1 C, the dilatometer was
left in the bath and a 1 C step change was pro-
grammed. The specic thermal histories used are
detailed below. The standard deviation of the mean
temperature over a period of 3.5 days is 0.003 C;
however, the bath temperature is only reported to
0.01 C due to the data acquisition system used.
The time for temperature equilibration was
found to be 120 s for both temperature jumps
(from one bath to another and for the temperature
perturbations). Time zero for the jumps is taken as
the time at which the temperature change is initi-
ated. Although some authors have advocated the
use of various other time zeros [2,33,48], modeling
work from our laboratory has shown that for the
cooling history in the dilatometric experiments,
taking time zero at the beginning of the nite
quench results in insignicant error in data com-
pared to the results of a perfect quench for times
greater than approximately two times the thermal
equilibration time [49]. Taking time zero at the
beginning of the quench has been previously sug-
gested by Struik [50].
2.3. Thermal histories
The material was equilibrated at a temperature
T0 above Tg to erase all previous thermal histories.
For down jump experiments, the sample is quen-
ched from T0 to 96 C and the evolution of volume
at 96 C is monitored for 80 000 s. The down
jump is shown in the schematic Fig. 3 by path ab.
For the memory experiments [2], the sample is
quenched from T0 to a temperature T1 below Tg
and kept at T1 for time t1 such that upon reheating
to 96 C, the material is at approximately zero
departure from equilibrium. The evolution of the
volume at 96 C is then monitored for 80 000 s.
The path acde in the schematic Fig. 3 repre-
sents a memory experiment. It is noted that Fig. 3
shows the down jump and memory experiments
for a perfect quench. In reality the glass line after
a quench is lower than that indicated on the
schematic. However, as mentioned above, the
474 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480

 R t b 
 R t b #

dt
dt
Tf T0 DTa 1
e 0 s DTp 1
e tp s
;

6
where DTp Tp
Ta and tp is the time at which the
temperature perturbation is applied. Although se-
quential perturbations were performed, the time
between each one is at least twice the aging time so
that they do not aect one another and can be an-
alyzed independently. The time integral from 0 to t
of 1=s in Eq. (6) can be divided into two integrals:
Z t Z tp Z t
dt dt dt
7
0 s 0 s tp s

and the rst integral on the right side of the Eq. (7)
can be rewritten as a function of departure from
equilibrium dp , using Eq. (1):
Fig. 3. Schematic curve of the evolution of volume with tem- Z tp
 1=b
dt d0
perature showing the thermal histories presented in this paper. ln ; 8
0 s dp
Table 1
Thermal histories for all experiments
where dp is the departure from equilibrium at Ta at
time tp when the perturbation experiment is star-
T0 (C) T1 (C) t1 (h)
ted. The second integral on the right side of Eq. (7)
Down jumps
can be simplied since s is essentially constant
104
102 during the perturbation due to the short duration
100 of the perturbation relative to the time of aging;
98 that is, the structural recovery taking place during
Memory experiments the perturbation does not cause a signicant shift
104 85 30 in the characteristic relaxation time. With this
104 80 70 assumption it follows that
104 75 160 Z t
dt t
tp
; 9
tp s sp
evolution of volume after a nite quench is indis-
tinguishable to that of a perfect quench for times where sp is the value of the relaxation time during
greater than twice the thermal equilibration time the perturbation. Substituting the expressions in
[49]. Table 1 shows the specic values of T0 , T1 and Eqs. (7)(9) into Eq. (6), the evolution of Tf during
t1 used in our experiments. Perturbations were the perturbation is then given by
2 h  i1=b
b 3
performed as in schematic Fig. 2 from 96 to 95 C.
d0 t
tp
6
ln dp sp 7
2.4. Data analysis Tf T0 DTa 641
e
7
5

Eq. (1) shows the expected response to a single
t
t b 

temperature jump from a temperature T0 to an
aging temperature Ta , in terms of ctive tempera-
ture Tf . In addition to the down jump, the tem-
perature perturbation is taken into account by
adding another term:

spp
DTp 1
e : 10
Eq. (10) can be rewritten in terms of departure
from equilibrium using Eq. (4). After simplica-
tion, the departure from equilibrium during the
 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480 475

perturbation at the perturbation temperature can We note that the results of the analyses of the
be written perturbations performed at the shortest aging
2 h  i1=b
b 3 times (te  1500 and 3000 s) are not presented
6

d0
ln d
t
tp
sp  t
tp
 b
7 because the time scale of the perturbation (being
dTp
Da6 DTp e sp 7
p

4DTa e 5: 0.1te ) was not long enough to give unique values of
sp and b.
11
2.5. Methodology validation
To derive the equation used to analyze the
perturbations from the memory experiments, an- To validate our data analysis (Eq. 11) we sim-
other term was added to Eq. (6) taking into ac- ulated data for down jump experiments using the
count the up-jump. TNM model and various model parameters. The
2  R b 3 simulations consisted of a down jump from 104 to


t
dt 96 C followed by three temperature perturbations
4
Tf T0 DTa 1
e 0 s 5
to 95 C at times 3600, 10 800 and 32 400 s from
2 R b 3 2 R b 3 the start of the initial jump. Eq. (11) was then used


t
dt

t
dt to t the response to these perturbations in a
DT1 41
e t1 s 5 DTp 41
e tp sp 5; manner similar to that used for data obtained with
the automated dilatometer.
12 Fig. 4 shows the correlation between the char-
acteristic relaxation time values found using the
with t1 being the time at the beginning of the up-
methodology derived above with those expected
jump and DTa Ta
T0 ; DT1 T1
Ta ; DTp
for three dierent model simulations. The expected
Tp
T1 , using the same notation as in Fig. 2.
values are the average lnsp during the perturba-
Carrying on a development similar to the one
tions. The TNM parameters used in the modeling
above, we obtain
are shown on the gure as well as the line where
 
b b lnsp calculated lnsp expected. The error in sp
dTp
Da DT0 e
ABC DT1 e
BC DTp e
C ;
b

is at most 4% indicating that the data analysis is

13 consistent with the TNM model.
where

 1=b Z tp
d0 dt t
tp
A ln ; B ; C :
dp t1 s sp
The ts were performed using KaleidaGraph
from Synergy Software, which utilizes the Leven-
bergMarquardt tting algorithm. The values of
d0 =d were obtained from the data at the beginning
of each perturbation. The data were tted a rst
time allowing the non-exponentiality parameter, b,
to vary and tting for sp for the down jump ex-
periments. For the memory experiments, both sp
and B were obtained from the t. b was found
to vary from 0:48  0:03 to 0:55  0:05 to in a
non-systematic way, while B varies for each per-
turbation since it is a function of the time of the Fig. 4. Correlation between the characteristic relaxation time
perturbation. The b values were averaged (b values found using Eq. 11 for perturbations simulated during
0:52) and the data was retted using this value of b. volume recovery after jumping from 104 to 96 C.
476 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480

3. Results and discussion

3.1. Cooling studies

Fig. 5 shows the specic volume versus tem-

perature curve obtained on cooling at a rate of
about 0.2 C/min. The thermal expansion coe-
cient is calculated to be 5:2  10
4 K
1 in the liquid
state and 2:0  10
4 K
1 in the glassy region. These
values agree with our previous work [32] and with
values [38,5154] found in the literature. The glass
transition temperature is determined as the inter-
cept of the glass and liquid lines. A value of 94.5 C
was found (at 0.2 C/min) which is similar to the
value of 94.8 C observed previously [32].
3.2. Eect of temperature perturbation on underly-
ing recovery
In order to use the perturbations as a probe of
the volume relaxation response, the underlying
volume relaxation should be unaected by the
temperature perturbations. Fig. 6 shows the vol-
ume recovery of the PS sample for two runs. The
initial temperature, T0 , is 104 C and the aging
temperature is 96 C for both runs. The line rep-
resents the response to a simple down jump while
the data points are the response to a down jump
with temperature perturbations to 95 C. The g-
Fig. 6. Departure from equilibrium at 96 C during volume
recovery of PS. The line is the volume recovery without tem-
perature perturbations, and the points show the response when
sequential temperature perturbations were performed to 95 C
during the recovery. For both runs, T0 104 C and Ta 96
C.
ure demonstrates that the perturbations do not
aect the underlying recovery since the two runs
are identical within experimental error. Note that
the responses to the perturbation up jumps (from
95 back to 96 C) were not recorded.
To further conrm that the temperature per-
turbations do not aect the underlying volume re-
covery, we t the underlying response with the
TNM model and compared the results to that ob-
tained in previous work [32] on the same polymer.
The results are summarized in Table 2. Both the
present and previous ts were performed assuming
a nite (rather than innite) temperature quench.
The values obtained for the tting parameters
Dh=R, x and b are similar to those obtained in
Ref. [32], indicating that the perturbations do not

Table 2
TNM parameters comparison
Parameter Model ts of the Results from
underlying recovery Ref. [32]
Dh=R (kK) 138.3 146.1
x 0.2 0.1
b 0.80 0.70
lnA=s
366.9
387.40
Fig. 5. Volume evolution of polystyrene on cooling at 0.2 C/
logs1 =s at 96 C 3.4 3.6
min.
 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480
signicantly aect the underlying volume recovery
of our sample. The value of lnA diers slightly
due to the dierence in Dh=R. The value of the
logarithm of the equilibrium relaxation time cal-
culated at 96 C is lower by 0.2 in this work.
3.3. Volume recovery
The volume recovery response depends on the
magnitude of the temperature jump as indicated
by Eq. (1). Fig. 7 shows the recovery of the sample
at 96 C for initial temperatures (T0 ) ranging from
104 to 98 C. Temperature perturbations of 1 C
from 96 C to 95 C were performed during each
run. The departure from equilibrium is greatest for
the highest T0 . The curves approach equilibrium
asymptotically and overlap at long times as ex-
pected, based on the extensive data set of Kovacs
[2]. Before analyzing the response to the tempera-
ture perturbations, we rst look at the results of
the memory experiments.
For memory experiments, the volumetric re-
sponse is more complicated, as shown in Fig. 8.
The thermal histories for the memory experiments
are indicated on the gure. Also shown is the re-
sponse to the simple down jump to 96 C with
T0 104 C. In all cases, the volume response was
measured at 96 and 1 C perturbations were per-
formed. For the memory experiment, the depar-
Fig. 7. Departure from equilibrium at 96 C during volume
recovery of PS for down jumps from T0 to Ta 96 C. Tem-
perature perturbations were performed to 95 C.
477
Fig. 8. Departure from equilibrium at 96 C for polystyrene in
response to memory experiments with the temperature history
104T1 96 C and to a down-jump from 10496 C. Tempera-
ture perturbation were performed to 95 C.
ture from equilibrium at 96 C is initially near
zero, then increases and nally returns to zero. The
overshoot increases as T1 decreases. The responses
converge to that of the down jump and approach
equilibrium asymptotically at long times. These
results are consistent with those of Kovacs who
attributed the overshoot to a memory eect im-
plying the existence of a distribution of charac-
teristic relaxation times [2].
3.4. Response to perturbations
We are interested in whether the characteristic
relaxation time depends only on the instantaneous
state of the material or on the time/temperature
history. To get this information, we examine the
volume response to the temperature perturbation.
Fig. 9 shows the departure from equilibrium d
versus time of the perturbation for a down jump
from 104 to 96 C and for a memory experiment
from 1048596 C for several perturbations. d is
dened here, as the departure from equilibrium at
95 C. We emphasize that in order to examine only
the response to the perturbation, we subtracted the
underlying relaxation from the response. Fig. 9
shows that, as expected, the volumetric response to
the 1 C temperature perturbation changes with d,
shifting to longer times with decreasing d. When
478 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480

tting the two experiments, along with the tting

error, are also shown.
By combining all of the data sets, we can now
examine the dependence of the characteristic re-
laxation time for volume on the value of d aver-
aged over the duration of the perturbation for
various thermal histories, as shown in Fig. 10. The
error bars in the gure represent the error in the t
of sp obtained using Eq. (11) or Eq. (13) for b
0:52. Independent of the thermal history, the data
suggest that the characteristic relaxation time does
depend on the departure from equilibrium d, as the
TNM and KAHR models assume.
It is noted that in the initial analysis, the data
Fig. 9. Departure from equilibrium at the perturbation tem-
points with the history 1048096 C were nearly a
perature (95 C) versus time of the perturbation for a down full logarithmic unit lower than the rest of the
jump from 104 to 96 C and for a memory experiment from data points and the d versus log time perturba-
1048596 C for several perturbations performed during aging tion responses were systematically shifted to values
at 96 C. For clarity the underlying recoveries have been sub- smaller than expected. Shifting these up by 6 
tracted. The continuous and dashed lines represent the ts to
the KWW equation as explained in the text, for the down jump
10
5 in d resulted in perturbation response curves
and memory experiment respectively. and s values that agreed with the rest of the data.
The systematic error cannot be explained by an
error in the temperature measurements. Using the
the system achieves equilibrium, the shape of the value of the thermal expansivity in the glass ob-
response and therefore the value of sp are identical tained from previous work [32] we calculate that
for all curves independent of the thermal history of to obtain a shift of 6  10
5 in d would require a
the sample. More importantly, the volumetric re-
sponse to the perturbations appears to be inde-
pendent of the path, i.e., the down jump and
memory experiments show the same response to
the perturbations at a given initial departure from
equilibrium. The data are representative of the
temperature histories examined in this work.
We can quantify the evolution of the volumetric
response to the 1 C perturbation by tting the
data as described earlier. However, in this exam-
ple, since the underlying recovery curve have been
subtracted from the perturbation responses, Eqs.
(11) and (13) simplify to a simple Kolrausch
WilliamsWatts equation (KWW) [55,56] for the
case where the perturbation does not aect the
underlying response:
 b
t
tp

Fig. 10. Dependence of the characteristic relaxation time for
dp
DTp Da e : 14
sp
volume on the departure from equilibrium for aging at 96 C
following various thermal histories. The solid line represents the
The ts to the KWW are shown as lines for the linear t of the data. The dashed line represents the result based
down jump and as dashed lines for the memory on the ts of the underlying curves with the parameters shown
experiment in Fig. 9. The sp values averaged from in Table 2.
 P. Bernazzani, S.L. Simon / Journal of Non-Crystalline Solids 307310 (2002) 470480
change in the perturbation temperature of 0.3 C,
which was not observed. Although it is unclear
why we had this problem with one of the seven
temperature histories we examined, we believe the
correction made is reasonable. Backing this up is
the fact that the data from the memory experi-
ments in which T1 was lower (75 C) and higher (85
C) both lie on the lns versus d line where the
majority of data points are located.
In Fig. 10, the slope of the lns versus d rela-
tionship is related to the KAHR parameters:
 
d lns 1
xH

; 15
dd Ta Da
where H Dh=RT 2 and T is the temperature. In
Fig. 10, this slope is
7920  1000. A value of

2400  800 (the dashed line in Fig. 10) was cal-
culated using our TNM model ts to the under-
lying recoveries and using Da 3:2  10
2 K
1
(Table 2). Alternatively, using the value of Dh=R of
138.3 kK, we calculated x
1:6 from the slope of
lns versus d. The values obtained from this
analysis and the t to the underlying recovery are
inconsistent. A possible explanation could be that
the use of temperature perturbations to follow the
characteristic relaxation time focuses on the short
time scale response. As a consequence, the TNM
parameters in Table 2, which were found by ana-
lyzing the complete relaxation curve, might be
underestimating the rate of relaxation at very short
times. This has been reported for systems far from
equilibrium where the TNM model is incapable of
tting the data [19,57].
Another explanation for the apparent discrep-
ancy between the strong dependence of lns on d
and the value of Dh=R for the TNM equation is that
the relationship between the characteristic relax-
ation time and the departure from equilibrium is
non-linear. Such non-linear relationships have
been derived from AdamGibbs theory [58] by
both Hodge and Scherer [8,59]. In other words, a
linear extrapolation of the lns versus d relation-
ship leads to values of lns at d0 which are much
smaller than would be expected. A natural way to
satisfy this is with a relationship between the two
variables that is not linear. This contrasts with the
assumption commonly made in the TNM/KAHR
479
models, although it is by no means necessary, that
the relationship between lns and Tf or between
lns and d is linear. We note that Schick and co-
workers [60] have recently found that they were
only able to well describe the loss and storage heat
capacity obtained from slow temperature-modu-
lated DSC cooling scans by using a nonlinear re-
lationship based on Adam and Gibbs.
4. Conclusion
This paper presents the development of a new
methodology capable for the rst time of fol-
lowing the evolution of the characteristic relax-
ation time for volume during the volume recovery.
Preliminary results are reported for a PS glass.
This methodology, analogous to the protocol
popularized by Struik for creep measurements,
uses sequential temperature perturbations that are
performed during the structural recovery of the
sample. The perturbations do not aect the un-
derlying volume recovery. For the thermal treat-
ments investigated, the characteristic relaxation
time for volume appears to depend on the instan-
taneous state of the material. The slope of
lns
versus d is 7920, considerably larger than expected
based on this and previous modeling of intrinsic
isotherms of the same material. In addition, the
analysis suggests that the relationship between
lns and d may not be linear as d varies from d0 to
0 in contrast to the assumption commonly made in
the TNM/KAHR models.
Acknowledgements
The authors gratefully acknowledge fruitful
discussions with Cornelius Moynihan, Mark Edi-
ger and Gregory McKenna concerning this work.
Partial nancial support from the American Chemi-
cal Society Petroleum Research Fund 36003-AC7
is also gratefully acknowledged.
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